2024-03-28T15:56:18Zhttps://upcommons.upc.edu/oai/requestoai:upcommons.upc.edu:2117/1075482022-05-22T01:12:14Zcom_2117_15797com_2117_28577com_2117_4001com_2117_28579com_2117_3825com_2117_28581com_2117_3989com_2117_79762col_2117_3055col_2117_4004col_2117_3828col_2117_3992col_2117_79840openAccess
Influence of exposure time on mechanical properties and photocuring conversion ratios for photosensitive materials used in additive manufacturing
Bonada Bo, Jordi
Muguruza Blanco, Asier
Fernández Francos, Xavier
Ramis Juan, Xavier
Universitat Politècnica de Catalunya. Departament de Resistència de Materials i Estructures a l'Enginyeria
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. REMM - Recerca en Estructures i Mecànica de Materials
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Energies: Termoenergètica
Additive Manufacturing
Material behavior
Mechanical properties
photopolymerization
Polimerització
Fabricació -- Automatització
Photopolymerization
The influence of UV post - curing process on mechanical properties as well as photocuring conversion ratios is presented. An analytical model to determinate the conversion ratio for frontal polymerization is used t o define 3D printing parameters in order to obtain a conversion profile as homogeno us as possible. The mechanical properties of 3D p rinted coupons with and without UV post - curing process were obtained through experimental tensile and bending tests. Furthermore, the experimental conversion ratios of printed samples were obtained by means of FTIR spectrometry analysis. It was observed that conversion ratios and some mechanical properties increase because of UV post - curing treatment, enabling the chance to optimize the whole manufacturing process in function of the 3D printed part requiremen ts.
2017-09-12T10:18:37Z
2017-09-12T10:18:37Z
2017
Conference report
2351-9789
http://hdl.handle.net/2117/107548
Bonada, J., Muguruza, A., Fernandez-Francos, X., Ramis, X. Influence of exposure time on mechanical properties and photocuring conversion ratios for photosensitive materials used in additive manufacturing. A: Manufacturing Engineering Society International Conference. "Proceedings of the 7th Manufacturing Engineering Society International Conference: Vigo (Spain), June 2017". Vigo: 2017.
eng
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Open Access
https://upcommons.upc.edu/bitstream/2117/107548/5/FULL%20PAPER%20MESIC2017-BONADA.pdf.jpg
oai:upcommons.upc.edu:2117/3744352023-07-30T01:58:08Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840openAccess
Stress-relaxing thermosets with easily regulated bond exchange kinetics
Konuray, Ali Osman
Moradi, Sasan
Fernández Francos, Xavier
Serra Albet, Maria Àngels
Ramis Juan, Xavier
Morancho Llena, José María
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física
Poly(acrylate)
Poly(thiol-ene)
Thermosets
Epoxy
Polímers
Polymers
We have carried out stress-relaxation experiments on poly(acrylate) and poly(thiol-ene) based thermosets prepared from in-house synthesized epoxy-acid adducts with acrylate (for the former) and ene functionalities (for the latter). The adducts contain disulphide bonds at their center which allow their cured thermosets to undergo disulphide metathesis when heated above a certain temperature [1]. The possibility of concurrent transesterification, albeit at a significantly lower rate, between ester and hydroxyl moieties present in the components is not discarded
2022-10-14T10:08:48Z
2022-10-14T10:08:48Z
2022
Conference lecture
https://www.gep-slap2020.eu/abstracts
http://hdl.handle.net/2117/374435
Konuray, O. [et al.]. Stress-relaxing thermosets with easily regulated bond exchange kinetics. A: XVI Reunión del Grupo Especializado de Polímeros. XVII Simposio Lationoamericano de Polímeros. XV Congreso Iberoamericano de Polímeros. "GEP - GEP-SLAP 2022 - XVI Reunión del Grupo Especializado de Polímeros. XVII Simposio Lationoamericano de Polímeros. XV Congreso Iberoamericano de Polímeros". 2022, p. 248-249.
eng
info:eu-repo/grantAgreement/AEI/PN2021-2024/PID2020-115102RB-C22
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Open Access
2 p.
https://upcommons.upc.edu/bitstream/2117/374435/5/Stress%20relaxingl.pdf.jpg
oai:upcommons.upc.edu:2117/3763112022-11-20T03:12:34Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Nous politiouretans hibrids tipus vitrimèric. sintesi i caracterització
Guerrero, Federico
Flor López, Sílvia de la
Ramis Juan, Xavier
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física
Materials polimèrics
Vitrimers
Polímers
Polímers
Polymers
La preparació de materials híbrids orgànics-inorgànics és una de les estratègies utilitzades per millorar les propietats mecàniques i obtenir materials polimèrics d’altes prestacions. Aquest materials combinen la duresa i resistència de la fase inorgànica, i l’elasticitat i la rigidesa de la matriu orgànica. D’altra banda els vitrimers son polímers entrecreuats amb grups funcionals intercanviables, que permeten llur reciclatge, llur canvi de forma i en molt casos l’autoreparació.
2022
Conference lecture
http://hdl.handle.net/2117/376311
Guerrero, F. [et al.]. Nous politiouretans hibrids tipus vitrimèric. sintesi i caracterització. A: Trobada de Joves Investigadors dels Països Catalans. "Dotzena Trobada de Joves Investigadors dels Països Catalans". 2022, p. 1.
cat
https://scq.iec.cat/?p=10015
info:eu-repo/grantAgreement/AEI/PN2021-2024/PID2020-115102RB-C22
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Restricted access - publisher's policy
1 p.
oai:upcommons.upc.edu:2117/3621702022-02-13T05:15:30Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Dual-curing of (meth)acrylate-epoxy thiol formulations
Roig, Adrià
Ramis Juan, Xavier
Flor López, Sílvia de la
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física: Termodinàmica
Thiol-(meth)acrylate
Thermal thiol-epoxy
Homopolymerization
Trimethylolpropane
Polímers
Termodinàmica
Polymers
Thermodynamics
We have implemented a sequential photo-thermal dual-curing procedure based on glycidylmethacrylate/trimeth(acrylate)/thiol mixtures. The first step of the curing process is a radical UV-initiated thiol-(meth)acrylate reaction, and the second is a thermal thiol-epoxy step catalysed by a base. Since (meth)acrylates can lead to homopolymerization by radical mechanism, the amount of thiol has to be optimized to reach cross-linked materials with Tgs above room temperature and good mechanical performance. At the same time a thermal thio-Michael reaction can occur, especially when acrylates are present in the formulation. If the amount of thiol is too low, epoxy homopolymerization can also take place
2021
Conference lecture
https://www.aim.it/epfschool2021/program
http://hdl.handle.net/2117/362170
Roig, A. [et al.]. Dual-curing of (meth)acrylate-epoxy thiol formulations. A: European Polymer Federation Summer School 2021. "Abstract book EPF Summer School 2021". 2021,
eng
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
oai:upcommons.upc.edu:2117/910582022-06-14T05:55:18Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Curado “Click” secuencial de mezclas tiol-acetoacetato-acrilato, catalizada por una fotobase latente
Ramis Juan, Xavier
Konuray, Ali Osman
Liendo Castillo, Freddy Jesus
Fernández Francos, Xavier
Morancho Llena, José María
Salla Tarragó, José María
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Enginyeria dels materials: Materials plàstics i polímers
Àrea temàtica UPC: Enginyeria química: Química física
Plàstics termostables
Heat resistant plastics
2016
Conference lecture
978-84-16283-26-2
http://hdl.handle.net/2117/91058
Ramis, X., Konuray, A., Liendo, F.J., Fernandez-Francos, X., Morancho, J., Salla, J., Serra, À. Curado “Click” secuencial de mezclas tiol-acetoacetato-acrilato, catalizada por una fotobase latente. A: Reunión del Grupo Especializado de Polímeros (GEP) de la RSEQ y RSEF. "XIV Reunión del grupo especializado de polímeros (GEP) de la RSEQ y RSEF. Avances en materiales poliméricos: Burgos, España: 5-8 de septiembre 2016". Burgos: 2016, p. 261-263.
spa
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
3 p.
oai:upcommons.upc.edu:2117/3761792022-11-20T04:01:06Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
New bio-based poly(acylhydrazone) vitrimers: synthesis and characterization
Roig, Adrià
Ramis Juan, Xavier
Flor López, Sílvia de la
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física
Polímers
Polymers
2022
Conference lecture
http://hdl.handle.net/2117/376179
Roig, A. [et al.]. New bio-based poly(acylhydrazone) vitrimers: synthesis and characterization. A: 13 th Spanish-Italian Symposium on Organic Chemistry. "13 th Spanish-Italian Symposium on Organic Chemistry. Book of Abstracts". 2022, p. P2-10.
eng
info:eu-repo/grantAgreement/AEI/PN2021-2024/PID2020-115102RB-C22
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Restricted access - publisher's policy
oai:upcommons.upc.edu:2117/3761772022-11-20T04:18:29Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Appplication of renewable thiols in the preparation of poly(thiourethane) covalent adaptable networks
Guerrero, Federico
Ramis Juan, Xavier
Flor López, Sílvia de la
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física
Renewable thiols
Poly(thiourethane)
Polímers
Polymers
One of the industries most dependent on fossil fuels is the polymer industry: over 99% of
polymer production uses monomers derived from oil and gas. For this reason, polymers
derived from biomass (biopolymers) are widely developed. Different monomers derived from
biomass have been proposed in the last decades: lignin, saccharides, vegetable oils, and
terpenes, among others.
On the other hand, thermosetting polymers are advantageous in a broad range of industrial
applications due to their chemical and thermal resistance and excellent mechanical
performance. However, once finished their useful life, due to the impossibility of being
recycled, they become an environmental problem, being incineration or landfill the only
solutions.
A new family of polymeric materials is being developed to solve thermosetting recycling issues,
starting from renewable materials. They present a covalent adaptable network structure
(vitrimeric materials) whose topology can be changed by thermally activated reversible
chemical processes. These reversible reactions allow this type of cross-linked polymers'
reprocessing and recycling and exhibit other excellent characteristics such as self-healing or
self-welding properties
2022
Conference lecture
http://hdl.handle.net/2117/376177
Guerrero, F. [et al.]. Appplication of renewable thiols in the preparation of poly(thiourethane) covalent adaptable networks. A: 13 th Spanish-Italian Symposium on Organic Chemistry. "13 th Spanish-Italian Symposium on Organic Chemistry. Book of Abstract". 2022, p. P1-1.
eng
info:eu-repo/grantAgreement/AEI/PN2021-2024/PID2020-115102RB-C22
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Restricted access - publisher's policy
oai:upcommons.upc.edu:2117/914642022-06-14T05:55:10Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
New thermosets from cycloaliphatic epoxy resin by thiol-epoxy click reaction
Guzman, Dailyn
Mateu, Blai
Fernández Francos, Xavier
Ramis Juan, Xavier
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Enginyeria dels materials: Materials plàstics i polímers
Resines epoxídiques
Plàstics termostables
Epoxy resins
Heat resistant plastics
2016
Conference lecture
http://hdl.handle.net/2117/91464
Guzman, D., Mateu, B., Fernandez-Francos, X., Ramis, X., Serra, À. New thermosets from cycloaliphatic epoxy resin by thiol-epoxy click reaction. A: International Conference on Nanostructured Polymers and Nanocomposites. "Abstracts book – IXth ECNP International Conference on Nanostructured Polymers and Nanocomposites: Rome, Italy: September 29-31, 2016". Roma: 2016, p. 1-3.
eng
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
3 p.
oai:upcommons.upc.edu:2117/811302022-06-14T05:55:13Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Sequential UV/thermal processing of acrylate-epoxy clearcoats
Ye, Lishi
Fernández Francos, Xavier
Morancho Llena, José María
Serra Albet, Maria Àngels
Ramis Juan, Xavier
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Enginyeria dels materials: Materials plàstics i polímers
Acrylate
Epoxy
Dual curing
Resines epoxídiques
Epoxy resins
B-stage processing is a term used for one-pot thermosetting formulations that can be partially cured or pre-dried, after being applied to a substrate and then cured under heat and pressure. B-staging has processing advantages that can be exploited in assembly processes, especially the possibility of splitting the different steps of a process in a production line, in terms of time and location, thus helping to prevent manufacturing bottlenecks. However, in B-stage processing the pre-drying process has usually tight time and temperature constraints that make necessary a careful control to avoid over-drying leading to loss of properties such as adhesion and material waste. Alternative dual-curing procedures aim at eliminating the above drawbacks while keeping and even enhancing their processing advantages [1-3]. Further advantage comes from the possibility of tailoring the material structure and properties between both curing stages by changing the formulation composition. This represents a significant advantage over conventional B-stage, in which the material properties in the intermediate stage are kinetically controlled, depending on temperature/time and vitrification. This approach opens a new way for flexible processing, not just in terms of curing stageability but also in terms of the intermediate material characteristics (adhesion, flowing ability, rigidity,…). In addition, the latent character of the second curing stage ensures good storage stability between both curing stages.
In this work, the sequential UV/thermal processing of acrylate-epoxy clearcoats is studied. Mixtures of methacrylates/acrylates with different side chain and functionality, at least one of them bearing an epoxy group, are photocured to obtain a linear or cross-linked polymer that is subsequently post-cured at elevated temperatures to obtain the final cross-linked material. A combination of a radical photoinitiator and a cationic thermal latent initiator is used in order to permit sequential controlled curing. Different formulation compositions are examined in order to analyze the possibility of custom-tailoring the structure and properties between both curing stages and at the end of the process. The sequential UV-curing and thermal curing processes are studied with photoDSC, FTIR/ATR and DSC. The thermal-mechanical properties of the materials in the intermediate and final states are assessed with DMA, DSC and TGA. The potential application of this curing process is also illustrated.
[1] K. Studer, C. Decker, E. Beck, R. Schwalm, Eur. Polym., J. 41 (2005) 157
[2] J. A. Carioscia, J. W. Stansbury, C. N. Bowman, Polymer, 48 (2007) 1526
[3] C. F. Carlborg, A. Vastesson, Y. Liu, W. van der Wijngaart, M. Johansson, T. Haraldsson, J. Polym. Sci. A: Polym. Chem., 52 (2014) 2604
2015
Conference lecture
978-3-940237-34-7
http://hdl.handle.net/2117/81130
Ye, Lishi, Fernandez-Francos, X., Morancho, J., Serra, À., Ramis, X. Sequential UV/thermal processing of acrylate-epoxy clearcoats. A: Central and Eastern European Conference on Thermal Analysis and Calorimetry. "Book of abstracts: 3rd Central and Eastern European Conference on Thermal Analysis and Calorimetry: CEEC-TAC3: 25-28 August 2015, Ljubljana, Slovenia". Ljubljana: 2015, p. 325.
eng
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
1 p.
oai:upcommons.upc.edu:2117/3619932022-05-19T11:04:37Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Sequential photo-thermal curing of (meth)acrylate-epoxy thiol formulations
Roig, Adrià
Flor López, Sílvia de la
Ramis Juan, Xavier
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física: Termodinàmica
UV-initiated thiol-(meth)acrylate reaction
Thermal thiol-epoxy
Homopolymerization
Termodinàmica
Thermodynamics
In this work, a novel dual-curing procedure has been developed. It is a combination of a first radical UV-initiated thiol-(meth)acrylate reaction, followed by a second thermal thiol-epoxy step catalysed by a base. Since (meth)acrylates can lead to homopolymerization by radical mechanism, the amount of thiol have to be optimized to reach crosslinked materials with Tgs above room temperature and good mechanical performance. It should be considered, that if the amount of thiol is too low, epoxy homopolymerization can take place. The use of glycidyl methacrylate in combination with trifunctional meth(acrylates) allow this system to gel in the 1st stage and avoid possible dripping or exudation of free monomers in the storage of the intermediate materials. We selected trimethylolpropane tris(3-mercaptopropionate) as the thiol, 2,2-dimethoxy-2- phenylacetophenone as UV initiator and 1-methylimidazole as the base catalyst
2021
Conference lecture
https://www.vesps2021.net/program/list-of-poster-presentations
http://hdl.handle.net/2117/361993
Roig, A. [et al.]. Sequential photo-thermal curing of (meth)acrylate-epoxy thiol formulations. A: Virtual European Symposium of Photopolymer Sciences. "Book of abstract Virtual European Symposium of Photopolymer Sciences". 2021,
eng
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-82849-C2-2-R/ES/MATERIALES TERMOESTABLES AVANZADOS OBTENIDOS MEDIANTE METODOLOGIA CLICK/
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
oai:upcommons.upc.edu:2117/3623382022-05-19T11:09:27Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Novel hybrid poly(thiourethane)/POSS covalent adaptable networks
Guerrero, Federico
Flor López, Sílvia de la
Ramis Juan, Xavier
Santos, Jose-Ignacio
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física: Termodinàmica
High-performance polymeric
Thiols
Poly(thiourethane)
Thermal conductivity
Polímers
Polymers
Hybrid organic-inorganic materials have been introduced as one of the strategies to improve mechanical properties and obtaining new high-performance polymeric materials. These materials present a synergism that meets the advantages of both organic and inorganic phases: hardness and strength of inorganic phase, and elasticity and toughness of the organic matrix [1] Thiols and isocyanate groups react to give thiourethane or thiocarbamate groups. Polythiourethane (PTUs) are analogous with sulphur of polyurethane (PUs), one of the most produced polymers in the world. Despite of their advantages over PUs, PTUs have been less studied than PUs. In previous studies of our group, it was demonstrated that trans-thiocarbamoylation exchange reactions between thiourethane groups leads to a vitrimeric-like behaviour to this knd of networked polymers improving the easily of recycling and reshaping them [2, 3]. The aim of this study is not only to improve the mechanical characteristics of PTUs but also to determine the effect of the inorganic reinforcement in the relaxation behaviour.
2021
Conference report
https://www.aim.it/epfschool2021/program
http://hdl.handle.net/2117/362338
Guerrero, F. [et al.]. Novel hybrid poly(thiourethane)/POSS covalent adaptable networks. A: European Polymer Federation Summer School 2021. "Abstract book EPF Summer School 2021". 2021,
eng
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-82849-C2-2-R/ES/MATERIALES TERMOESTABLES AVANZADOS OBTENIDOS MEDIANTE METODOLOGIA CLICK/
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
oai:upcommons.upc.edu:2117/812082022-06-14T05:55:16Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Thermal curing of an epoxy-anhydride system modified with hyperbranched poly(ethylene imine)s with different terminal groups
Morancho Llena, José María
Fernández Francos, Xavier
Acebo Gorostiza, Cristina
Ramis Juan, Xavier
Salla Tarragó, José María
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Enginyeria dels materials: Materials plàstics i polímers
Epoxy networks
thermal curing
hyperbranched modifiers
kinetics
Calorimetria
Resines epoxídiques
Calorimetry
Epoxy resins
Epoxy resins are widely used in applications such as adhesives, coatings, electric laminates, encapsulation of semiconductor devices, matrix material for composites, structural components and cryogenic engineering because of their mechanical properties, adhesion and chemical resistance.
However, epoxy resins are inherently brittle due to their high cross-link density. To increase their toughness different modifiers such as rubber, thermoplastic and glass particles can be added, but they always limit the processability of the formulation. Hyperbranched polymers (HBP) are a new kind of polymers used as modifiers of epoxy resins to increase their toughness, but they maintain the processability of the formulation due to their highly branched dendritic structure, which is a key point in coatings applications [1-2].
In this paper, the influence of three hyperbranched poly(ethylene imine) polymers with different terminal groups (two of them with t-butyl terminal groups and the other one with phenyl groups) on the thermal curing of an epoxy-anhydride system has been studied. The synthetic procedure to prepare the polymeric modifiers is quite easy and it consists in reacting commercial poly(ethylene imine) with the corresponding isocyanate in chloroform solution at room temperature. The epoxy resin and the anhydride we selected are Epikote 828 and 4-methyl hexahydrophtalic anhydride, respectively. As initiator we have used N,N-dimethylbenzylamine [3]. The techniques employed in this study have been DSC (differential scanning calorimetry) and DMTA (dynamic mechanical thermal analysis). The kinetics of the thermal curing has been analyzed using isoconversional methods.
The addition of the hyperbranched polymers with t-butyl terminal groups hardly changes the thermal curing process of the epoxy-anhydride system, but if the poly(ethylene imine) with phenyl end-groups is added, the thermal curing of the system is decelerated.
In the systems studied, all the HBPs used decrease the glass transition temperature of the epoxy-anhydride system, acting therefore as plasticizers.
[1] B. Voit, J. Polym. Sci. A: Polym. Chem., 38 (2000) 2505
[2] L. Boogh, B. Pettersson, J.-A.E. Manson, Polymer, 49 (2001) 2249
[3] M. Flores, X. Fernández-Francos, F. Ferrando, X. Ramis, A. Serra, Polymer, 53 (2012) 5232
2015
Conference lecture
978-3-940237-34-7
http://hdl.handle.net/2117/81208
Morancho, J., Fernandez-Francos, X., Acebo, C., Ramis, X., Salla, J., Serra, À. Thermal curing of an epoxy-anhydride system modified with hyperbranched poly(ethylene imine)s with different terminal groups. A: Central and Eastern European Conference on Thermal Analysis and Calorimetry. "Book of abstracts: 3rd Central and Eastern European Conference on Thermal Analysis and Calorimetry: CEEC-TAC3: 25-28 August 2015, Ljubljana, Slovenia". Ljubljana: 2015, p. 324.
eng
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
1 p.
oai:upcommons.upc.edu:2117/3887862023-06-18T06:05:14Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840openAccess
Synthesis and characterization of new fully bio-based poly(acylhydrazone) vanillin vitrimers
Roig, Adrià
Petrauskaité, Aina
Ramis Juan, Xavier
Flor López, Sílvia de la
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Enginyeria química
Materials resistents al foc
Fire resistant materials
New acylhydrazone vitrimeric-type materials have been studied. These materials can be efficiently relaxed, without the addition of an external catalyst, through an exchange process that has been confirmed as imine metathesis, which differs from the previously reported transimination process in linear polymers. This is the first article that develops vitrimers with high Tg and fast relaxation based on poly(acylhydrazone)s. These materials have been prepared by condensing stoichiometric amounts of glycidyl vanillin and aliphatic dihydrazides of different chain lengths. The curing reaction takes advantage of the different reactivity of formyl and glycidyl groups and proceeds in two sequential steps: a first condensation of the formyl group of vanillin with dihydrazide monomers at low temperature followed by reaction of the remaining hydrazides with the epoxide, which requires temperatures above 150 °C. The complete disappearance of the initial reactive groups has been confirmed by FTIR spectroscopy. The thermomechanical characteristics have been evaluated by DMTA, obtaining Tgs above 100 °C for the materials prepared, which present excellent vitrimeric features with very short relaxation times. Using model compounds, we were able to demonstrate that imine metathesis is responsible for the exchange process. The thermal stability of these materials has been rated by TGA. Poly(acylhydrazone) materials showed good recycling and self-healing abilities and could be hydrolyzed in an acidic medium.
2023-06-16T07:17:08Z
2023-06-16T07:17:08Z
2022
Conference lecture
https://pubs.rsc.org/en/content/articlelanding/2022/py/d1py01694f
http://hdl.handle.net/2117/388786
Roig, A. [et al.]. Synthesis and characterization of new fully bio-based poly(acylhydrazone) vanillin vitrimers. A: Bordeaux Polymer Conference 2022. "Bordeaux Polymer Conference 2022. Book of Abstracts". 2022, p. 197.
eng
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Open Access
1 p.
https://upcommons.upc.edu/bitstream/2117/388786/3/PY_d1py01694f_edit_report%20%281%29.pdf.jpg
oai:upcommons.upc.edu:2117/3744462022-10-16T06:31:38Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840openAccess
Preparation of New Vitrimeric Materials Based on Glycidyl Vanillin-imines
Roig, Adrià
Petrauskaité, Aina
Ramis Juan, Xavier
Flor López, Sílvia de la
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física
Environment
Polymers
Thermal properties
Mechanism
Vitrimers
Polímers
Polymers
Objectius de Desenvolupament Sostenible::13 - Acció per al Clima
The current exponential growth of the human population is associated with a degradation of the environment. In terms of lack of degradability and persistence in the environment, increasing attention is being paid to polymers. Among them, thermosets, that become hardened in the curing, lead to infusible networks with high strength and solvent resistance and superior mechanical and thermal properties. On the downside, their use raises a severe environmental concern because the covalent linkages in the network are irreversible, preventing recycling. An alternative that overcomes this issue is the use of dynamic covalent chemistry, which relies on chemical processes causing reversible formation and breaking of covalent bonding in response to stimuli and allows obtaining easily recyclable thermosets while retaining the overall polymer structure. Incorporating reversible groups like imines in the network structure can allow the reprocessing and recycling of these materials, maintaining their mechanical performance. The associative mechanism of the imine interchange leads to these materials being included in the group of vitrimers. In our work, the inclusion of the imine groups in the network is based on the use of a diglycidyl diimine obtained from vanillin. This renewable product is condensed with 4,4’-oxydianiline to form the bisphenol-diimine, and then it is reacted with epichlorohydrin to obtain the epoxy-imine monomer with the following structure.
2022-10-14T11:49:17Z
2022-10-14T11:49:17Z
2022
Conference lecture
http://hdl.handle.net/2117/374446
Roig, A. [et al.]. Preparation of New Vitrimeric Materials Based on Glycidyl Vanillin-imines. A: Bordeaux Polymer Conference 2022. "Bordeaux Polymer Conference 2022. Book of Abstracts". 2022, p. 253.
eng
info:eu-repo/grantAgreement/AEI/PN2021-2024/PID2020-115102RB-C22
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Open Access
1 p.
https://upcommons.upc.edu/bitstream/2117/374446/5/Vitrimeric.pdf.jpg
oai:upcommons.upc.edu:2117/273502022-09-11T08:14:58Zcom_2117_15797com_2117_28577com_2117_403099com_2117_28579com_2117_1553com_2117_3965com_2117_3917com_2117_21311com_2117_28581com_2117_7029com_2117_3307com_2117_3474com_2117_79762com_2117_3880com_2117_1536com_2117_28582com_2117_3935com_2117_3085col_2117_3055col_2117_403105col_2117_5865col_2117_3968col_2117_3920col_2117_21314col_2117_7032col_2117_3310col_2117_3477col_2117_79840col_2117_3883col_2117_7209col_2117_3938col_2117_3088openAccess
Criterios para prácticas de evaluación de calidad. Una propuesta de GRAPA-RIMA
Cadenato Matia, Ana María
Martinez, Maria
Amante García, Beatriz
Gallego Fernández, María Isabel
Jordana Barnils, José
Sánchez Robert, Francesc Josep
Farrerons Vidal, Óscar
Isalgué Buxeda, Antonio
Fabregat Fillet, Jaume
Universitat Politècnica de Catalunya. Departament de Projectes d'Enginyeria
Universitat Politècnica de Catalunya. Institut de Ciències de l'Educació
Universitat Politècnica de Catalunya. Departament d'Enginyeria Electrònica
Universitat Politècnica de Catalunya. Departament d'Expressió Gràfica a l'Enginyeria
Universitat Politècnica de Catalunya. Departament de Física Aplicada
Universitat Politècnica de Catalunya. Departament de Matemàtica Aplicada III
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Universitat Politècnica de Catalunya. GIIP - Grup de Recerca en Enginyeria de Projectes: Disseny i Sostenibilitat
Universitat Politècnica de Catalunya. DMAG - Grup d'Aplicacions Multimèdia Distribuïdes
Universitat Politècnica de Catalunya. e-CAT - Circuits i Transductors Electrònics
Universitat Politècnica de Catalunya. INSIDE - Innovació en Sistemes per al Disseny i la Formació a l'Enginyeria
Universitat Politècnica de Catalunya. AIEM - Arquitectura, energia i medi ambient
Àrea temàtica UPC: Ensenyament i aprenentatge: Ensenyament universitari
Àrea temàtica UPC: Ensenyament i aprenentatge: Gestió i planificació educativa: Avaluació educativa (avaluació del procés)
Criterios de evaluación
Rúbricas
Calidad
Ensenyament universitari
Education, Higher
El grupo de innovación GRAPA (GRupo de la Evaluación de la Práctica Académica) del
proyecto RIMA de la Universitat Politècnica de Catalunya ha elaborado una serie de criterios, en
forma de rúbrica, como buenas prácticas de evaluación, coherentes con la integración y
evaluación de competencias, exigencia en la implantación de los nuevos grados que se imparten
en los estudios superiores en las universidades españolas.
En la presente comunicación se podrá comprobar que además cualquier actividad de evaluación
que cumpla estos criterios en el máximo nivel de exigencia representa una actividad de calidad,
demostrando que se pueden tener asignaturas de calidad, objetivo común tanto de instituciones
como del profesorado y alumnado. Además en la presente comunicación se mostrarán algunos
ejemplos de estos criterios.
2015-04-15T11:12:05Z
2015-04-15T11:12:05Z
2012
2012
Conference report
9788499213002
http://hdl.handle.net/2117/27350
Cadenato, A. [et al.]. Criterios para prácticas de evaluación de calidad. Una propuesta de GRAPA-RIMA. A: Congrés Internacional de Docència Universitària i Innovació. "VII Congrés Internacional Docència Universitària i Innovació: La universitat: una institució de la societat = La universidad: una institución de la sociedad = The University: an institution of Society: Barcelona, 4, 5 i 6 de juliol, 2012 Universitat Pompeu Fabra". Barcelona: Octaedro, 2012, p. 1-21.
spa
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Open Access
21 p.
Octaedro
https://upcommons.upc.edu/bitstream/2117/27350/7/cidui2012_CV.pdf.jpg
oai:upcommons.upc.edu:2117/1063052021-05-21T04:39:40Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Comparative results between three protocols for achieving highly exfoliated epoxy-clay nanocomposites
Hutchinson, John M.
Shiravand, Fatemeh
Calventus Solé, Yolanda
Ferrando Piera, Francesc
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Enginyeria dels materials
Àrea temàtica UPC: Enginyeria mecànica
Nanoestructures
Nanocompostos (Materials) -- Proves
Nanostructures
Nanocomposites (Materials)--Testing
2013
Conference report
http://hdl.handle.net/2117/106305
Hutchinson, J.M., Shiravand, F., Calventus, Y., Ferrando, F. Comparative results between three protocols for achieving highly exfoliated epoxy-clay nanocomposites. A: International Conference on Modification, Degradation and Stabilization of Polymers. "NANOCOMPOSITES MoDeSt Workshop 2013 : Book of abstracts". Warsaw: 2013, p. 57-60.
eng
http://en.www.ichp.pl/attach.php?id=2055
Restricted access - publisher's policy
4 p.
oai:upcommons.upc.edu:2117/3619592022-05-19T11:31:11Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840openAccess
Dual-curable vitrimers for 3d-printing
Romano, Angelo
Konuray, Ali Osman
Roppolo, Ignazio
Sangermano, Marco
Fernández-Francos, Xavier
Ramis Juan, Xavier
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física: Termodinàmica
3D-printed
Acrylate homopolymerization
Epoxy-acid
Thermal curing
Impressió 3D
Termodinàmica
Three-dimensional printing
Thermodynamics
3D-printed objects can greatly benefit from the introduction of molecular structure undergoing dynamic bond exchange [1] or the use dual-curing processing [2], leading to a significant enhancement of mechanical properties and extended capabilities such as adhesion, reshaping, healing and recycling. We have developed a family of dual-curing 3D-printable materials based on acrylate homopolymerization for the printing stage and epoxy-acid reaction for the second thermal curing stage, with the purpose 1) having a stable intermediate material with desired reshaping and adhesion capabilities and 2) obtaining a network structure capable of undergoing dynamic work rearrangement promoted by transesterification between ester and available hydroxyl groups. A latent amine catalyst has been added in order to accelerate both the thermal curing stage and transesterification
2022-02-08T13:06:47Z
2022-02-08T13:06:47Z
2021
Conference lecture
https://www.vesps2021.net/program/list-of-oral-presentations
http://hdl.handle.net/2117/361959
Romano, A. [et al.]. Dual-curable vitrimers for 3d-printing. A: Virtual European Symposium of Photopolymer Sciences. "Book of Abstract Virtual European Symposium of Photopolymer Sciences". 2021,
eng
https://www.vesps2021.net/program/list-of-oral-presentations
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2017-82849-C2-2-R/ES/MATERIALES TERMOESTABLES AVANZADOS OBTENIDOS MEDIANTE METODOLOGIA CLICK/
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Open Access
https://upcommons.upc.edu/bitstream/2117/361959/3/262.pdf.jpg
oai:upcommons.upc.edu:2117/3744372022-10-16T09:11:44Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840openAccess
Synthesis and characterization of new fully bio-based poly(acylhydrazone) vanillin vitrimers
Roig, Adrià
Petrauskaité, Aina
Flor López, Sílvia de la
Ramis Juan, Xavier
Serra Albet, Maria Àngels
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Física
Thermosets
Polymers
Poly(acylhydrazone)
Vanillin
Vitrimers
Polímers
Polymers
In the present century the need to recycle thermosets to reach a sustainable environment has led a huge number of researchers to develop new reshapable networked polymers. In this scenario, vitrimers, materials able to change their topology via exchange of the covalent bonds, usually activated by thermal stimulus, are attracting growing interest. They can potentially be reshaped, self-welded, repaired and recycled at high temperature without appreciable degradation [1]. These materials behave as thermosets at room temperature but becomes malleable at high temperature when the exchange reaction occurs
2022-10-14T10:30:45Z
2022-10-14T10:30:45Z
2022
Conference report
https://www.gep-slap2020.eu/abstracts
http://hdl.handle.net/2117/374437
Roig, A. [et al.]. Synthesis and characterization of new fully bio-based poly(acylhydrazone) vanillin vitrimers. A: XVI Reunión del Grupo Especializado de Polímeros. XVII Simposio Lationoamericano de Polímeros. XV Congreso Iberoamericano de Polímeros. "GEP - GEP-SLAP 2022 - XVI Reunión del Grupo Especializado de Polímeros. XVII Simposio Lationoamericano de Polímeros. XV Congreso Iberoamericano de Polímero". 2022, p. 87-88.
eng
info:eu-repo/grantAgreement/AEI/PN2021-2024/PID2020-115102RB-C22
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
Open Access
2 p.
https://upcommons.upc.edu/bitstream/2117/374437/5/Ramis.pdf.jpg
oai:upcommons.upc.edu:2117/911002022-06-14T05:55:15Zcom_2117_15797com_2117_28577com_2117_3989com_2117_28579com_2117_79762com_2117_28581col_2117_3055col_2117_3992col_2117_79840
Nuevos termoestables obtenidos mediante procesos duales basados en reacciones tipo "Click" con tioles
Serra Albet, Maria Àngels
Ramis Juan, Xavier
Acebo Gorostiza, Cristina
Guzman, Dailyn
Belmonte-Parra, Alberto
Fernández Francos, Xavier
Flor López, Sílvia de la
Universitat Politècnica de Catalunya. Departament de Màquines i Motors Tèrmics
Universitat Politècnica de Catalunya. POLTEPO - Polímers Termoestables Epoxídics
Àrea temàtica UPC: Enginyeria dels materials: Materials plàstics i polímers
Àrea temàtica UPC: Enginyeria química
Plàstics termostables
Reaccions nuclears
Heat resistant plastics
Chemical reactions
2016
Conference report
978-84-16283-26-2
http://hdl.handle.net/2117/91100
Serra, À., Ramis, X., Acebo, C., Guzman, D., Belmonte-Parra, A., Fernandez-Francos, X., de la Flor, S. Nuevos termoestables obtenidos mediante procesos duales basados en reacciones tipo "Click" con tioles. A: Reunión del Grupo Especializado de Polímeros (GEP) de la RSEQ y RSEF. "Avances en materiales poliméricos: XIV Reunión del grupo especializado de polímeros (GEP) de la RSEQ y RSEF [5-8 de septiembre]: libro de resúmenes GEP2016". Burgos: 2016, p. 43-44.
spa
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
Restricted access - publisher's policy
2 p.